Oxyalkylated amine-modified thermoplastic phenol-aldehyde resins, and method of making same



OXYALKYLATED AMlNE-MODIFIED THERMO- PLASTIC PHENOL-ALDEHYDE RESINS, AND METHOD OF MAKING SAME Melvin De Groote, University Petrolite Corporation, of Delaware N Drawing. Application July 30, 1952, Serial No. 301,895

8 Claims. (Cl. 260-45) City, Mo, assignor to Wilmington, Del., a corporation The present invention is a continuation-in-part of my copending application, Serial No. 288,744, filed May 19, 1952. The present invention is concerned with derivatives obtained by the oxyalkylation, particularly the oxyethylation or oxypropylation, of certain resin condensates.

These resin condensates are described in detail in the aforementioned co-pending application, Serial No. 288,* 744, and are obtained by the process of condensing (a) an oxyalkylatioil-susceptible, fusible, non-oxygenated organie solvent-soluble, water-insoluble, low-stage phenolaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical, and (0) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heatstable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

Compounds or derivatives are obtained by the process of oxyalkylating said amine-modified resin condensates by a member selected from the class of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide. One aspect of the invention is, of course, the procedure for obtaining such oxyalkylation products.

In many instances and for various purposes, particularly for the resolution of petroleum emulsions of the water-inoil type, one may combine a comparatively large proportion of the alkylene oxide, particularly propylene oxide or a combination of propylene oxide and ethylene oxide, with a comparatively small proportion of the resin condensate. In some instances the ratio by weight has been as high as SO-to-l, i. e., the ultimate product of reaction contained approximately 2% of resin condensate and approximately 98% of alkylene oxide.

This invention in a more limited aspect as far as the reactants are concerned which are subjected to oxyalkylation are certain amine-modified thermoplastic phenolaldehyde resins. Such amine-modified resins are described in the aforementioned copending application and much that is said herein is identical with the text of said aforementioned copending application. For purpose of simplicity the invention, purely from a standpoint of the resin condensate involved, may be exemplified by an idealized formula as follows:

in which R represents an aliphatic hydrocarbon substituent generally having four and not over 18 carbon atoms but most preferably not over 14 carbon atoms, and It generally is a small whole number varying from 1 to 4. In the resin structure it is shown as being derived from formaldehyde although obviously other aldehydes are equally satisfactory. The amine residue in the above structure is derived from a nonhydroxylated basic polyamine and usually a strongly basic polyamine having at least one secondary amino radical and free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical, and may be indicated thus:

in which R represents any appropriate carbon-linked radical, such as an alkyl, alicyclic, arylalkyl radical, etc., free from hydroxyl radicals, with the proviso that at least one occurrence of R contains an amino radical which is not part of a primary amino radical or part of a substituted imidazoline radical or part of a substituted tetrahydropyrimidine radical. The term carbon-linked radical is intended to mean a radical attached to the nitrogen atom of the above formula by a bond from a carbon atom.

Actually, What has been depicted in the formula immediately above is only an over-simplified exemplification of that part of the polyamine which has the reactive secondary amino group. Actually, a more complete illustration is obtained by reference to substituted polyalkylene amines of the following structure:

RI! R! in which R has its prior significance, R" represents a hydrogen atom or radical R, D is a hydrogen atom or an alkyl group, n represents the numerals 1 to 10, and x represents a small whole number varying from 1 to 7 but generally from 1 to 3, with the proviso that the other previously stated requirements are met. See U. S. Patent No. 2,250,176, dated July 22, 1941, to Blair.

See also U. S. Patent No. 2,362,464, dated November 14, 1944, to Britton et al., which describes alkylene diamines and polymethylene diamines having the formula where R represents an alkyl, alkenyl, cycloalkyl, or aralkyl radical, and n represents a comparatively small integer such as 1 to 8.

GHz-OH:

wherein n'is a whole number from 2 to 12 inclusive, and the nitrogen atoms are separated by at least two carbon atoms, into a secondary amine by means of an alkylating agent such as dimethyl sulfate, benzyl chloride, an alkyl bromide, an ester of a sulfonic acid, etc., so as to yield a compound such as oar-om /H N-C Ha -41 CHr-Cn alkyl The introduction of two such p'olyainine radicals into a comparatively small resin 'molecule, for instance, one having'3 to'6 phenolic nuclei as specified, alters the re sultant product in a number of ways. In the first place, a basic nitrogen atom, of course adds a hydrophile effect; in the second place, depending on the size of the radical R, there may be a counterbalancing hydrophobe effect or one in which the hydrophobe effect more than counterbalances the hydrophile effect of the nitrogen atom. Finally, in such cases where R contains one or more oxygen atoms, another effect is introduced, particularly another hydrophile effect.

I am not aware that it has been previously suggested to modify resins of the kind herein described by oxyalkylation, such as oxyethylation or oxypropylation.

Referring again to the resins as such, it is Worth noting that combinations,- either resinous or otherwise, have been prepared from phenols, aldehydes, and reactive amines particularly monoamines.

Combinations, resinous or otherwise, have been prepared from phenols, aldehydes, and reactive amines, particularly amines having secondary amino groups. Generally speaking, such materials have fallen into three I classes; the first represents non-resinous combinations derived from phenols as such; the second class represents resins which are usually insoluble and used for the purpose for which ordinary resins, particularly thermo-setting resins are adapted. The, third class represents resins which are soluble as initially prepared but are not heatstable, i. e., they are heat-convertible, which means they are not particularly suited as raw materials for subsequent chemical reaction which requires temperatures above the boiling point of'water or thereabouts.

As to the preparation of the first class, i. e., nonresinous materials obtained from phenols, aldehydes and amines, particularly secondary amines, see United States Patents Nos. 2,2 18,739,dated October 22, 1940, to Bruson; 2,033,- 092, dated March 3, 1936, to Bruson; and 2,036,916, dated April 7, 1936, to Bruson.

As to a procedure by'which a resin is produced as such involving all three reactants and generally resulting in an insoluble resin, or in any event, a resin which becomes insoluble in presence of added formaldehyde or the like, see United States Patents Nos. 2,341,907, dated February 15, 1944, to Cheetham et al.; 2,122,433, dated July 5, 1938, to Meigs; 2,168,335, dated August 8, 1939, to Heckert; 2,098,869, dated November 9, 1937, to Harrnon etaL; and 2,211,960, dated August 20, 1940, to Meigs.

A third class of material which approaches the closest to the herein-described derivatives or resinous amino derivatives is described in U. S. Patent No. 2,031,557, dated February 18, 1936, to Bruson.

The resins employed as raw materials in the instant procedure are characterized-by the presence of an aliphatic radical in the ortho or para position, i. e., the phenols themselves are difunctional phenols. This is a differentiation from the resins described in the aforementioned Bruson Patent No. 2,031,557, insofar that said patent discloses suitable resins obtained from meta-substituted phenols, hydroxybenzene, resorcinol, p*,p"(dihydroxydiphenyl)-dimethylmethane, and the like, all ofwhich have at least three points of reaction per phenolic nuclei and as a result can yield resins which may be at least incipiently cross-linked even though they are apparently still soluble in oxygenated organic solvents or else are heat reactive insofar that they may approach insolubility or become insoluble dueto the effectof heat, or added formaldehyde, or both.

The resins herein employedcontain only two terminal groups which are reactive to formaldehyde, i. e., they are difunctional from the standpoint of methylol-forming reactions. As is well known, although one may start with difunctional phenols, and depending on the procedure employed, one may-obtain cross-linking-which indicates that one or more of the phenolic nuclei have been-convertedfrom a difunctional radical to a trifunctional radical, or in terms of the resin, the molecule as a whole has a methylol-forming reactivity greater than 2. Such shift can take place after the resin has been formed or during resin formation. Briefly, an example is simply where an alkyl radical, such as methyl, ethyl, propyl, butyl, or the like, shifts from an ortho position to a meta position, or from a para position to a meta position. For instance, in thecaseof phenol-aldehyde varnish resins, one can prepare at least some in which the resins, instead of having only two points of reaction can have three, and possibly more points of reaction, with formaldehyde, or any other reactant which tends to form a methylol or substituted methylol group.

Apparently there is no similar limitation in regard to the resins employed in the aforementioned Bruson Patent 2,031,557, for the reason that one may prepare suitable resins from phenols of the kind already specified which invariably and inevitably would yield a resin having a functionality greater than two in the ultimate resin molecule.

The resins herein employed are soluble in a non-oxygenated hydrocarbonsolvent, such as benzene or xylene. As pointed out in the aforementioned Bruson Patent 2,031,557, one of the objectives is to convert the phenolalde'hyde resins employed as raw materials in such'a way as to render them hydrocarbon soluble, i. e., soluble in benzene. The original resins'of US. Patent 2,031,557 are selectedonthe basis of solubility in-an oxygenated inert organicsolvent, such asalcohol or-dioxane. It is immaterial'wheth'er the resinshere employed are soluble in dioxane or alcohol, but they must be soluble inbenzene.

The resins herein employed as raw materials must be comparatively low molal products having on the average 3 to 6 nuclei per resin-molecule. The resins employed in the aforementioned U. S. Patent No. 2,031,557, apparently need not'rneet "any such limitations.

The condensation produ'ctshere obtained, whether in the form of the free base-or the salt, do-not go over to the insoluble stage on heating. This apparently is not true of the materials described in aforementioned Bruson Patent 2,031,557 and apparently one of the objectives with which 'the invention is concerned, is to obtain a heatconvertible condensation product. The condensation product obtained according to the present invention is heat stable and, in fact, one of 'its outstanding qualities is that it can be subjected to oxyalkylation, particularly oxyethylati'onor oxypropylation, under conventional conprecursors for subsequent reaction, yet as such and with I out further reaction, they have definitely valuable properties and uses as hereinafter pointed out.

What has been said bility,

i. e., presence of an alkaline catalyst, for example, any event at a temperature above 100 C. withpreviously in regard to heat sta particularly when employed as a refactant forprep-,

aration of derivatives, is stillyimportant from thestand-u point of manufacture of thejcondensation products jthemv selves insofar thatin the condensation process. employed in preparing the compounds described subsequently in detail, there is no objection to the employing of atemj perature above the boiling point of water. As a matter of fact, all the examplesincluded subsequently employ temperatures going up to 140 to 150 C. using resins of the kind described in U. S. 2,031,557 it appears desirableand perhaps If one were Patent No. absolutely necessary that the temperature be kept relatively low, for

instance, between C. and 100 C.-, and more specifically at a temperature of 80 to 90 C.jThe1'e is no such limitation in the condensation procedure herein described for reasons which are obvious in light of. What has been said previously.- e

What is said above deserves further amplification at this point for the reason thatit mayshorten what is said subsequently in regard to the production of the herein described condensation products. Aspointed out in the instant invention the resin selected is xylene or benzene soluble, which ditiere'ntiates the resins from those emanother way, It can be zero as wellasa whole number A ployed in the aforementioned Bruson Patent No, 2,031, 557. Since formaldehyde generally iseemployed' eco nomically in an aqueous cedure which will allow reactions. to take place at the interface of the two immiscible liquids, to wit, the fprmal- I dehyde solution andthe resin solution, onthe assumption that generally the amine will dissolve in one phase or the phase (30% to 40% ,solution, for example) it is necessary to have manufacturing proto another factor which other. Although reactions of the kind herein. described will begin at least at comparatively low temperatures, for g instance, 30 C., 40 C.,or C.,yet the reaction does not go to completion except bythe use of the higher temperatures. The use of higher temperatures means,- of course, that the condensation product obtained at the end of the. reaction must not be heat-reactive. Of course, one can add an oxygenated solvent such as alcohol, dioxane, various ethers of glycols, or the like, and produce a homogeneous phase. if this latter procedure is, employed in preparing the herein described condensations it is purely a matter of convenience, but whether it is or not, ultimately the temperature must still pass withinthe zone indicated elsewhere, i. e., somewhere'above the boil ing point of water unless some obvious equivalentprocedure is issued.

Any reference, as in the hereto appended claims, to the procedure employed in the-process is not intended to limit the method or order in which the reactants are added, commingled or reacted. The procedure has been referred to as a condensation process for obvious reasons. As pointed out elsewhere it is my preference to dissolve the resin in a suitable solvent, add the amine, and then add the formaldehyde as a 37% solution. However, all three reactants can be added in any order. I am inclined to believe that in the presence of a basic catalyst, such as the amine employed, that the formaldehyde producesv methylol groups attached to, the phenolic nuclei which, in turn, react with the amine. It would be immaterial,

of course, if the formaldehyde reacted with the amine so as to introduce a methylol group attached to nitrogen which, in turn, would react with the resin molecule. Also, it would be immaterial if both types of compounds were formed which reacted with each other with the evolution h of a mole of'formaldehyde available for further reaction.

the ethoxy, glyc ide, ethylene oxide, propylene oxide orthe like,and n' isa number varying from 1 to 60, with the proviso oxyalkylate; all the available phenolic of which and Furthermore, a reaction could take place in which three different molecules are simultaneously involved although, for theoretical reasons, that is less likely. What is said herein in this respect is simply by way of explanation to avoid any limitation in regard to the appended claims Since the amines herein employed are nonhydroxylated itis obvious the amine-modified resin is at least susceptible to oxyalkylation by virtue of the phenolic hydroxyl radi 1 e cats. Referring to the idealized formula which appeared previously it is obvious the oxyalkylated derivatives, or atleast a substantial portion of them, could be indicated I in the following manner:

in which R"O is the radical of alkylene oxide, such as propoxy or similar radicals derived from that one need not hydroxyl radicals. In other words, one need only convert two phenolic hydroxyl radicals per resin molecule. Stated subject to what has been said immediately preceding, all will be considered in greater detail subsequently.

Actually, what has been said as complete an idealized presentation as is desirable due this: Although the polyamine is non-hydroxylated and may have a tertiary amine group which is not susceptible to oxyalltylation, it may have morethan one secondary amino group as, for example, in the case of tetraethylene group may or may not be susceptible to pentamine. Such oxyalkylation under the conditions described, for reasons which are obscure.

Briefly stated, oxyalkylation seems to proceed readily at available Whichare readily susceptible to oxyalkylation.

contains a plurality of secondary amino the condensate can be depicted more satisfactorily in the following manner by first referring to the resin condensate then to the oxyalkylated derivative:

at the phenolic hydroxyl but also at one or more of the available secondary amino groups when they appear.

This can be depictedin the following manner:

previously may not be? may be involved. Thefactor is terminal secondary amino groups but less rapidly and sometimes hardly at allwhen the same group appears in the center ofa large molecule. In the instant situation there are phenolic hydroxyls whole number, with inwhiclifor. simplicity the formula just shown previous- 1y,.has. beenzlimitedto .the specific. instance where there is one. oxyalkylation-susceptible secondary amino radical as part of the polyamine residue. In the above formula R"O is the radical of an alkylene oxide such as the ethoxy, propoxy or similar radicals derived from glycide, ethylene oxide, propylene oxide, .or'the like, and n is a number varying from 1 to 60, with theproviso that one need not oxyalkylate all theavailable phenolic hydroxyl radicals or all the available amino:hydrog en atoms to the extent they are present. In other. words, one need convert only, two labile hydrogen radicals per condensate. it is immaterial whether thelabile hydrogen atoms be attached to oxygen or nitrogen.

One important use of the herein described products is in,the. resolution .of.petroleum emulsions of the water-in- As fa1t;as,the.use;of the herein described products goes forqpurpose;.of resolution of petroleum emulsions of the Water-in-oil. type, I particularly prefer. to use those which as .suchorzin, the form of.the fr'ee base or hydrate, i. e., combination-with water or particularly in the form of a low molalrorg anicv acid. such as the acetate or hydroxy. acetate, havesufliciently hydrophile. character to at least meet .thetests. set forthinU. S. Patent No. 2,499,368,- dated.March ,7, 195.0, to DeGroote et al. In said patent such testfor-emulsification using. a water-insoluble solvent, generallyxylene isdescribed. as an index of surface ac-. tivity. v I v .Imthepresent instancethevarious condensation prod-. uctszas. such .or in the/form ofthe free base or in the form of..the. acetate, may -not necessarily-be xylene-soluble although they arein'many instances. If such compounds are notrxylene-soluble thezobvious chemical equivalent orequivalent chemical testcan :be made by simply using somesuitable.solvent, preferably a water-soluble solvent such as.ethylenetglycol diethylether, or a low molal alcohol, or amixtureto dissolve the appropriate product being examinedeand. then mix'with' the equal weight of xylene,followed.-by.additionofiwater. Such test is obviously the samezfor. thereason that-there will be two phaseson vigorous shaking and surface activity makes its presence manifest; Ibis understood the reference in the hereto appendedgclaims as to the use of xylene in the ern-ulsificationv test I includes such obvious variant.

Reference is again made. to U. S.- Patent 2,499,368 dated March 7, 1950, to De Groote and Keiser. In said immediately aforementioned patent the following test appears:

The same is true in regard to the oxyalkylate resins herein specified;- particularly in the. lower stage of oxyalkylation; the so-called sub-surface active stage. The. surface-active properties arereadily demonstrated by producing a xylene-water emulsion. A suitable procedure is as follows: The oxyalkylated resin is dissolved in an equal weight of xylene. Such 50-50 solution is then mixed with l-3 'volumes of water'and shaken to produce an emulsion. The amount of xylene isinvariably suflicient to reduce even -a tacky-resinous'product to a solution which is readilydispersible; The emulsions so produced are usually xylene-in-wateremulsions (oil-in-water type) particularly whentthe amount of distilled water used is at least slightly-in excesswof- -thevolumeof xylene solution and also if shakenvigorously; Attimes, particularly in the lowestsstagevof .oxyalkylation; one may-obtain. a waterin-xylene emulsions.(water-in-oilftype) which is apt to reverse on morewvigorous; shaking and further dilution resin molecule.

weight of xylene, Wlll serve to illustrate the above emulw with water. If inwdoubt as tothis. property, comparison with a resin obtained from para:tertiary butylphenol and.

formaldehyde (ratio .1 partphenol to 1.1 formaldehyde). using an acid catalyst and. then followed byoxyalkylationusingl moles of ethylene oxidefor-leach phenolichydroxyl, is helpful.

sification test.

in a few instances, the resinmay not be sufficiently, solu-.

ble in xylene alone but may. require the. addition of some i ethylene glycol diethylether as, described elsewhere. It" is understoodthat suchmixture,or any other similarmixv. ture, is considered theequivalent of xylene for the purpose.

ofthisjtest. 7

In many cases, there is no doubt as to the presenceor absence of hydrophile or surface-active characteristics in I the products used in accordance with this invention. They dissolve or disperse inwater; and such dispersionsfoam:

readily. With borderline cases, i. e., those which. show only incipienthydrophile or surface-active property (subsurface-activityl tests for emulsifyingproperties or self.-

dispersibility are useful. The fact that a reagent is capable of producing a dispersion in water is proof that it is distinctly hydrophile.

uct on mere dilution inatest-tube exhibits self emulsifi cation. For this reason,; if it is desirable to determine the approximate point where self-emulsification begins-,..

then it is better to eliminate the xylene or equivalent. from a small portion ofthe reaction mixture and. test such portion- In some cases, such.xylene-free resultant may showinitialor incipient hydrophile properties,-whereas in presence of xylene such properties would notbe noted. In other cases, the. first objective indication of hydrophile properties may be thecapacity of thematerial. to emulsify an insolublesolvent. such .as xylene- It isto be emphasized that hydrophile properties herein referred to are such as those exhibited by incipient self-emulsifi-- cation or thepresence of emulsifying properties and go through the rangeof homogeneous. dispersibility or ad.- mixture with watereven in presence of added water.-. insoluble solvent and minor proportions of common .OlfiCe trolytes as occur .in oil field" brines.

Elsewhere, it ispointed. out that anemulsificationwtest may be used to determine. ranges. ofsurfacesactivity and 1 that suchv emulsification tests employ-axylene solution:

Statedranother way, ,it is really immaterial whethena.

xylene solution produces asol or: whether: it merely'pro duces an emulsion.

Having described the invention brieflyend'not necessarily in its most'complete aspect, the text'immediately'" following will be a more complete description'with' specific.

reference to reagents and the method of'manufacture.

For convenience the subsequent text will be divided into five parts:

Part1 is concerned with thegeneral structure of .theamine-modified resin condensatesand also the resin'itselfp which isused as a'raw material;

Part 2 is concerned with-appropriatew basic secondary polyamines freei from a hydroxyl radicabwhich :may. be?

Such 'resinprior to oxyalkylationl. I has a molecular weight indicatingabout 4 /2 units per.-

Such' resin, when; diluted. with. an. equal In doubtful. cases,- comparison? can be madewith thev butylphenol-formaldehyde resin.

9 employed in the preparation of the herein described amine-modified resins or condensates;

Part 3 is concerned with the condensation reactions involving the resin, the amine, and formaldehyde to produce the specific products or compounds;

Part 4 is concerned with the oxyalkylation of the products described in Part 3, preceding; and

Part 5 is concerned with uses for the products outlined in Part 4, preceding.

In the subsequent text, Parts 1, 2, and 3 appear in substantially the same form as in the text of aforementioned co-pending application, Serial No. 288,742, filed May 19, 1952 for both purpose of convenience and comparison.

PART 1 It is well known that one can readily purchase on the open market, or prepare, fusible, organic solventsoluble, water-insoluble resin polymers of a composition approximated in an idealized form by the formula an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to 14 carbon atoms, such as a butyl, amyl, hexyl, decyl, or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

Because a resin is organic solvent-soluble does not mean it is necessarily soluble in any organic solvent. This is particularly true where the resins are derived from trifunctional phenols as previously noted. However, even when obtained from a difunctional phenol, for instance para-phenylphenol, one may obtain a resin which is not soluble in a nonoxygenated solvent, such as benzene, or xylene, but requires an oxygenated solvent such as a low molal alcohol, dioxane, or diethylglycol diethylether. Sometimes a mixture of the two solvents (oxygenated and nonoxygenated) will serve. See Example 9a of U. S. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser.

The resins herein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or xylene. This presents no problem insofar that all that is required is to make a solubility test on commercially available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned U. S. Patent No. 2,499,365, or in U. S. Patent No. 2,499,368 dated March 7, 1950, to De Groote and Keiser. In said patent there are described oxyalkylation-susceptible, fusible, nonoxygenated-organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resins having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula 10 I in which R is aliphatic hydrocarbon radical having at least 4 carbon atoms and not more than 24 carbon atoms, and substituted in the 2,4,6 position.

If one selected a resin of the kind just described previously and reacted approximately one mole of the resin with two moles of formaldehyde and two moles of a basic nonhydroxylated secondary polyamine as specified, following the same idealized over-simplification previously referred to, the resultant product might be illustrated thus:

H H H O H E El R R n R I The basic polyamine may be designated thus:

subject to what has been said previously as to the presence of at least one secondary amine radical in at least one occurrence of R with the proviso, as previously stated, that the amine radical be free from a primary amine radical, a substituted imidazoline radical or a substituted tetrahydropyrimidine radical. However, if one attempts to incorporate into the formula f amine will be depicted as R! HN subject to the limitation and explanation previously noted.

In conducting reactions of this kind one does not necessarily obtain a hundred per cent yield for obvious reasons. Certain side reactions may take place. For instance, 2 moles of amine may combine with one .mole of the aldehyde, or only one mole of the amine may combine with the resin molecule, or even to a very slight extent, if at all, 2 resin units may combine without any amine in the reaction product, as indicated in the following formulas:

OH OH OH OH OH OH H H H H H C C-- C- C- O O O O U H R R n R R n R v.11 As has beenpointed out previously, as far as the resin unit' goesmnecan use-a'mole of aldehyde otherthan formaldehydasuchas acetaldehyde, propionaldehyde or butyraldehyde. The resin'unit' may be exemplified thus:

OH [OH I OH m R!!!- in which R is the divalent radical obtained from the particular aldehyde employed to form the resin. For

reasons which are obvious the condensation product obtained appears to be described best in terms of the method of manufacture.

As previously stated the preparation of resins, the kind herein employed as reactants, is well known. See previously mentioned U. S. Patent 2,499,368. Resins can be made using an acid catalyst or basic catalyst or a catalyst having neither acid nor basic properties in the ordinarysenseor without'any catalyst at all. It is'preferable' that the resinsernployedbe substantially neutral. ln'other words, if prepared'by using a strong acid as a catalyst, such'strong' acid should be neutralized. Similarly if a'strong' baseis used as a catalyst it is preferable that thebase be neutralizedalthough l have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of a free base. The amount may be as small as a 200th of a percent and as much as a few 10ths of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However; the mostdesirable procedure in practically every case is to have the resin neutral.

In preparing resins one does not get a single polymer, i. e., one having just 3 units, or just 4 units, or just 5 units, or just 6 units, etc. 'It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some' -trimer and pen-tamer present. Thus, the molecular weightsmaywbeusuch that it corresponds to a fractional value fornas, for example, 3.5, 4.5 or 5.2.

-In the. actualmanufacture of the resins I found no reason for using other than those-which are lowest in price and most readily available commercially. For purposes of convenience suitable resins are characterized in the following table:

TAB LE I 60 M01. wt. of resin molecule R derived Position of R from- N onyl Tertiary butyl. Seeondarybutyl. Cyelohexyl Tertiary amyl I -Mixed secondary and t e rt 1 a ry Formaldehyde d0 summon-woo d0 Butyraldehyde. do

..d0 Pglopionalde- Tertiary amy 12 PART 2 As has been pointed out, the amine hereinemployed as a reactant is .abasic secondary polyarnine and .preferably a strongly basic secondary polyarnine free from hydroxyl groups, free from primary amino groups, free from substituted imidazoline groups, and free from substituted tetrahydropyrimidine groups, in which the hydrocarbonradicals present, whether monovalent or divalent are alkyl, alicyclic, arylalkyl, or heterocyclic in character.

Previous reference has been made to a number of polyamines which are satisfactory for use as reactants in the instant condensation-procedure. The cheapest amines available are polyethylene amines and polypropylene amines. In the case of the polyethylene amines there may be as many as 5, 6 or 7 nitrogen atoms. Such amines are susceptible to terminal'alkylation or the equivalent, i. e., reactions which convert the terminal primary amino group or-groups into a secondary or tertiary-amine radical. In the case of polyamines having at least 3 nitrogen atoms or more, both terminal groups could be converted into tertiary .groups, or one terminal group could be converted! into a tertiary group and the other into a secondary amine group. By way of example the following formulas are included. It will be noted they include some polyamines which, instead of being obtained from dichloride, propylene dichloride, or the like, are obtained from dichloroethyl ethers in which the divalent radical has'a carbon-atom chain interrupted by an oxygen atom:

Honztmonerm H Another ,procedurefor producing suitable polyamines is. a reaction involving'firstan alkylene imine, such as ethylene imineor propylene imine, followed'by an ,alkylating'. agent oftherkind described, for example, dirnethylsulfateyorelse a reactionwhich involves an alkylene oxide; such as ethylencoxide. or propylene oxide, followed by the use of. an alkylating .agent or the comparable procedure in which a halide used.

What has been said previously may be illustrated. by reactions involving-a secondary alkyl amine, or a secondary aralkyl amine, or a secondary alicyclic amine, such as dibutylamine, dibenzylarnine, dicyclohexylamine, or mixed amines with an irnine so as to introduce a primary amino group which can be reacted with an alkylating 13 agenhsuch as dimethylsuifate. in a somewhat similar procedure the secondary amine of the kind just specified can be reacted with an alkylene oxide such as ethylene oxide, propylene oxide, or the like, and then reacted with an imine followed by the final step noted above in order to convert the primary amino group into a secondary amino group.

Reactions involving the same two classes of reactants previously described, i. e., a secondary amine plus an imine plus an alkylating agent, or a secondary amine plus an alkylene oxide plus an irnine plus an alkylating agent, can be applied to another class of primary amines which are particularly desirable for the reason that they introduce a definite hydrophile effect by virtue of an ether linkage, or repetitious ether linkage, are certain basic polyether amines of the formula:

in which at is a small whole number having a value of 1 or more, and may be as much as 10 or 12; n is an integer having a value of 2 to 4, inclusive; m represents the numeral 1 to 2; and m represents a number to 1, with the proviso that the sum of m plus m equals 2; and R has its prior significance, particularly as a hydrocarbon radical.

The preparation of such amines has been described in the literature and particularly in two United States patents, to wit, U. S. Nos. 2,325,514, dated July 27, 19 43, to Hester, and 2,355,337, dated August 8, 1944, to

Spence. The latter patent describes typical haloalkyl ethers such as oH oH2 E2 HCH2OC2H4OO2H4BI' 021150 (321110 C2H4O 0211400215401 Such haloalkyl ethers can react with ammonia, or with a primary amine such as methylamine, ethylamine, cyclohexylamine, etc., to produce a secondary amine of the kind above described, in which one of the groups attached to nitrogen is typified by R. Such haloalkyl ethers also can be reacted with ammonia to give secondary amines as described in the first of the two patents mentioned immediately preceding. Monoamines so obtained and suitable for conversion into appropriate polyamines are exemplied by (Ci-IsOCHzCI-lzCHzCHzCHzCI-lz)zNH.

Other somewhat similar secondary monoamines equally suitable for such conversion reactions in order to yield appropriate secondary amines, are those of the composition as described in U. S. Patent No. 2,375,659, dated May 8, 1945, to Jones et al. In the above formula R may be methyl, ethyl, propyl, amyl, octyl, etc.

Other suitable secondary amines which can be converted into appropriate polyamines can be obtained from products which are sold in the open market, such as may be obtained by alkylation of cyclohexylmethylamine or the .alkylation of similar primary amines, or for that matter,

amines of the kind described in U. S. Patent No. 2,482,546, dated September 20, 1949, to Kaszuba, provided there is no negative group or halogen attached to the phenolic nucleus. Examples include the following: betaphenoxyethylamine, gamma-phenoxypropylamine, betaphenoxy-alpha-methylethylamine, and beta-phenoxy-propylamine.

Other secondary monoamines suitable for conversion into polyamines are the kind described in British Patent No. 456,517 and may be illustrated by In light of the various examples of polyamines which have been used for illustration it may be well to refer again to the fact that previously the amine was shown as NpropyleneNpropyleneN In the first of the two above formulas if the reaction involves a terminal amino hydrogen obviously the radicals attached to the nitrogen atom, which in turn combines with the methylene bridge, would be different than if the reaction took place at the intermediate secondary amino radical as differentiated from the terminal group. Again, referring to the second formula above, although a terminal amino radical is not involved it is obvious again that one could obtain two diiferent structures for the radicals attached to the nitrogen atom united to the methylene bridge, depending whether the reaction took place at either one of the two outer secondary amino groups, or at the central secondary amino group. If there are two points of reactivity towards formaldehyde as illustrated by the above examples it is obvious that one might get a mixture in which in part the reaction took place at one point and in part at another point. Indeed, there are well known suitable polyamine reactions where a large variety of compounds might be obtained due to such multiplicity of reactive radicals. This can be illustrated by the following formula:

es represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, al-

though it may be so illustrated in an idealized simplification, it is difiicult to actually depict the final product of the cogeneric mixture except in terms of the process itself.

Previous reference has been made to the fact that the procedure herein employed is comparable, in a general way, to that which corresponds to somewhat similar derivatives made either from phenols as differentiated from a resin, or in the manufacture of a phenol-amine-aldehyde resin; or else from a particularly selected resin and an amine and formaldehyde in the manner described in Bruson Patent No. 2,031,557 in order to obtain a heat-reactive resin. Since the condensation products obtained are not heat-convertible and since manufacture is not restrictedto asingle phase system-arid since temperatures up to 150 C. -or thereaboutsmay be employed, it is obvious that the procedure-becomes comparatively simple. Indeed, perhaps no description is necessary over and above what has been said previously, in light of subsequent examples. However, for purpose of clarity the following details are included.

A convenient-piece of equipment for preparation of these cogeneric mixtures is a resin pot of the kind described in aforementioned U. S. Patent No. 2,499,368. In most instances the resin selected is not apt to be a fusible liquid at the early or low temperature stage of reaction if employed as subsequently described; in fact, usually it is apt to be a solid at distinctly higher temperatures,for instance, ordinary room temperature. Thus, I havefound it convenient to use a solvent and particularly one which can be removed readily at a comparatively moderate temperature, for instance, at 150 C. A suitable solvent is usually benzene, xylene, or a comparable petroleum -hydrocarbon or a mixture of such orsimilar solvents. Indeed, resins which are not soluble except in oxygenated solvents or mixtures containing such solvents are not here included as raw materials. The reaction can be conducted in such a way that the initial reaction, and perhaps the bulk of the reaction, takes place in a polyphase system. However, if desirable, one can use an oxygenated solvent such as a low-boiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcohols. can be used or one can use a comparatively. nonvolatile solvent such as dioxane or the diethylether of ethyleneglycol. One can also use a mixture of benzene or xylene and such oxyenated solvents. Note that the use ofsuch oxygenated solvent is not required in the sense that it is not necessary to use an initial resin which is soluble only in an oxygenatedsolvent as just noted, and it is not necessary to have a single phase system for reac- .tion.

Actually, .water is apt to be present as a solvent for the reason that in most cases aqueous formaldehyde is employed, which may be the commercial product which is approximately 37%, or it may be diluted down to about 30% formaldehyde. However, para-formaldehyde can be used but it is more diflicult perhaps to add a solid material instead of the liquid solution and, everything else being equal, the latter is apt to be more economical. In any event, water is present as water of reaction. If the solvent is completely removed at the end of the process, no problem is involved if the material is used for any subsequent reaction. However, if the reaction mass is going to be subject to some further reaction where the solvent may be objectionable, as in the case of ethyl or hexyl alcohol, and if there is to be subsequent oxyalkylation, then, obviously, the alcohol should not be used orv else it should be removed. The fact that an oxygenated solvent need not be employed, of course, is an advantage for reasons stated.

Another factor, as far as the selection of solvent goes, is whether or not the cogeneric mixture obtained at the end -of the reaction .is to. be used as such or. in. the salt form. The cogeneric mixtures obtained are apt to be solids or thick viscous-liquids in which there is some change from. the initial resin itself, particularly if some ofthe initial solvent is apt to remain without complete removal. Even ifone starts with a resin which is almost water-white in color, the products obtainedare almost invariably a dark red in color or at least a red- :amber, or some color which includes both an amber component and a reddish component. By and large, the melting point is apt to be lower and the products may be more sticky and more tacky than the original resin itself.

Depending on the resin selected and on the amine selected the-condensation product or reaction mass on a solventf-ree basis may be hard, resinous and comparable to the resin itself.

The products obtained, depending on the reactants selected, may be water-insoluble or water-dispersible, or water-soluble, or close to being water-soluble. Water solubility is enhanced, of course, by making a solution in the acidified vehicle such as a dilute solution, for instance, a 5% solution of hydrochloric acid, acetic acid, hydroxyacetic acid, etc. One also may convert the finished product into salts by simply adding a stoichiometric amount of any selected acid and removing any water present by refluxing with benzene or the like. In fact, the selection of the solvent employed may depend in part whether or not the product at the completion of the reaction is to be converted into a salt form.

In the next succeeding paragraph it is pointed out that frequently it is convenient to eliminate all solvent, using a temperature of not over C. and employing vacuum, if required. This applies, of course, only :to those circumstances where it is desirable or necessary to remove the solvent. Petroleum solvents, aromatic sol vents, etc., can be used. The selection of solvent, such as benzene, xylene, or the like, depends primarily on cost, i. e., the use of the most economical solvent and also on three other factors, two of which have been previously mentioned; (a) is the solvent to remain in the reaction mass without removal? (b) is the reaction mass to be subjected to further reaction in which the solvent, for instance, an alcohol, either low boiling or high boiling, might interfere as in the case of oxyalkylationl; and the third factor is this, (0) is an effort to be made to purify the reaction mass by the usual procedure as, for example, a water-wash to remove the water-soluble unreacted formaldehyde, if any, 'or a water-wash to remove any unreacted water-soluble polyamine, if employed and present after reaction? Such procedures are well known and, needless to say, certain solvents are more suitable than others. Everything else being equal, I have found xylene the most satisfactory solvent.

I have found no particular advantage in using a low temperature in the early stage of the reaction because, and for reasons explained, this is not necessary although it does apply in some other procedures that, in a general way, bear some similarity to the present procedure. There is. no objection, of course, to giving the reaction an opportunity to proceed as far as it will at some low temperature, for instance, 30 to 40 but ultimately one must employ the highter temperature in order to obtain products of the kind herein described. If a lower temperature reaction is used initially the period is not critical, in fact, it may be anything from a few hours up to 24 hours. I have not found any case where it was neces sary or even desirable to hold the low temperature stage for more than 24 hours. In fact, I am not convinced there is any advantage in holding it at this stage for more than 3 or 4 hours at the most. This, again, is a matter of convenience largely for one reason. In heating and stirring the reaction mass there is a tendency for formaldehyde to be lost. Thus, if the reaction can be conducted at a lower temperature so as to use up part of the formaldehyde at such lower temperature, then the amount of unreacted formaldehyde is decreased subsequently and makes it easier to prevent any loss. Here, again, this lower temperature is not necessary by virtue .of heat convertibility as previously referred to.

If solvents and reactants are selected so the reactants and products of reaction are mutually soluble, then agitation is required only to the extent that it helps cooling or helps distribution of the incoming formaldehyde. This lected solvent, such as benzene or xylene. Refluxing should be long enough to insure that the resin added, preferablyin a powdered form, is completely soluble. However, if the resin is prepared as such it may be added in solution form, just as preparation is described in aforementioned U. S. Patent 2,499,368. After the resin is in complete solution the polyamine is added and stirred. Depending on the polyamine selected, it mayor may not be soluble in the resin solution. If it is not soluble in the resin solution it maybe soluble in the aqueous formaldehyde solution. If so, the resin then will dissolve in the formaldehyde solution as added, and if not, it is even possible that the initial reaction mass could be a threephase system instead of a two-phase system although this would be extremely unusual. This solution, or mechanical mixture, if not completely soluble is cooled to at least the reaction temperature or somewhat below, for example 35 C. or slightly lower, provided this initial low temperature stage is employed. The formaldehyde is then added in a suitable form. For reasons pointed out I prefer to use a solution and whether to use a commercial 37% concentration is simply a matter of choice. In large scale manufacturing there may be some advantage in using a 30% solution of formaldehyde but apparently this is not true on a small laboratory scale or pilot plant scale. 30% formaldehyde may tend to decrease any formaldehyde loss or make it easier to control unreacted formaldehyde loss.

On a large scale if there is any difiiculty with formaldehyde loss control, one can use a more dilute form of formaldehyde, for instance, a 30% solution. The reaction can be conducted in an autoclave and no attempt made to remove water until the reaction is over. Gen erally speaking, such a procedure is much less satisfactory for a number of reasons. For example, the reaction does not seem to go to completion, foaming takes place, and other mechanical or chemical difficulties are involved. I have found no advantage in using solid formaldehyde because even here water of reaction is formed.

Returning again to the preferred method of reaction.

and particularly from the standpoint of laboratory pro cedure employing a glass resin pot, when the reaction has proceeded as one can reasonably expect at a low temper ature, for instance, after holding the reaction mass with or without stirring, depending on whether or not it is homogeneous, at 30 or 40 C. for 4 or 5 hours, or at the i most, up to l0-24 hours, I then complete the reaction by raising the temperature up to 150 C., or thereabouts as required. The initial low temperature procedure can be eliminated or reduced to merely the shortest period of time which avoids loss of polyamine or formaldehyde. At a higher temperature I use a phase-separating trap and subject the mixture to reflux condensation until the water of reaction and the water of solution of the formaldehyde is eliminated. I then permit the temperature to rise to somewhere about 100 C.,, and generally slightly above 100 C., and below 150 C. by eliminating the solvent or part of the solvent so the reaction mass stays within this predetermined range. This period of heating and refiuxing, after the water is eliminated, is continued until the reaction mass is homogeneous and then for one to three hours longer. The removal of the solvents is com ducted in a conventional manner in the same way as the removal of solvents in resin manufacture as described in aforementioned U. S. Patent No. 2,499,368.

Needless to say, as far as the ratio of reactants goes I have invariably employed approximately one mole of the resin based on the molecular Weight of the resin molecule, 2 moles of the secondary polyamine and 2 moles of formaldehyde. In some instances I have added a trace of caustic as an added catalyst but have found no particular advantage in this. In other cases I have used a slight excess of formaldehyde and, again, have not found any particular advantage in this. In other cases I have used a slight excess of amineand, again, have not found any longer detectible the phaseparticular advantage in so doing. Whenever feasible I have checked the completeness of reaction in the usual ways, including the amount, of water of reaction, molecular weight, and particularly in some instances have checked whether or not the end-product showed surfaceactivity, particularly in a dilute acetic acid solution. The nitrogen content after removal of unreacted polyamine, if any is present, is another index.

In the hereto attached claims reference is made to the product as such, i. e., the anhydro base. Needless to say, the hydrated base, i.e., the material as it combines with water or the salt form,.with a combination of suitable acids as noted, is essentially the same material but is merely another form and, thus, the claims are intended to cover all three forms, i. e., the anhydro base, the free base, and the salts. r

In light of what has been said previously, little more need be said as to the actual procedure employed for the preparation of the herein described condensation products. The following example will serve by way of illustration:

Example 1b The phenol-aldehyde resin is the one that has been identified previously as Example 2a. it was obtained from a paratertiary butyl phenol and formaldehyde. The resin was prepared using an acid catalyst which was completely neutralized at the end of the reaction. The molecular weight of the resin was 882.5. This corre sponded to an average of about 3 /2 phenolic nuclei, as the value for n which excludes the 2 external nuclei, i. e., the resin was largely a mixture having 3 nuclei and 4 nuclei excluding the 2 external nuclei, or 5 and 6 overall nuclei. The resin so obtained in a neutral state had a light amber color.

882 grams of the resin identified as 2a preceding were powdered and mixed with a somewhat lesser weight of xylene, i. e., 600 grams. Themixture was refluxed until solution was complete. It was then adjusted to approximately 30 to 35 C. and 176 grams of symmetrical dimethylethylene diamine added. The mixture was stirred vigorously and formaldehyde added slowly. In this particular instance the formaldehyde used was a 30% solution and 200 grams were employed which were added in a little short of 3 hours. The mixture was stirred vigorously and kept within a temperature range of 30 to 46 C. for about 19 hours. At the end of this time it was refluxed, using a phase-separating trap and a small amount of aqueous distillate withdrawn from time to time. The presence of unreacted formaldehyde was noted. Any unreacted formaldehyde seemed to disappear within approximately two to three hours after refluxing started. As soon as the odor of formaldehyde was no separating trap was set so as to eliminate all the water of solution and reaction. After the water was eliminated part of the xylene was removed until .the temperature reached approximately 152 C. or slightly higher. The mass was kept at this higher temperature for three to four hours and reaction stopped.

During this time, any additional water which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stay in the cogeneric mixture. A small amount of the sample was heated on a water bath to remove the excess; xylene and the residual material was dark red in color and had the consistency of a sticky fluid or tacky resin. The overall time for reaction was somewhat less than 30 hours. In other examples, it varied from a little over 20 hours up to 36 hours. The time can be reduced by cutperiod to approximately 3 to 6 several hours. Then refluxing was employed until the odor of formaldehyde disappeared. After the odor of formaldehyde disappeared the phase-separating trap was employed to separate out all the Water, both the solution PART 4 in preparing oxyalltyiated derivatives of products of the kind which appear as examples in Part 3, I have found it particularly advantageous to use laboratory equipment and condensation. After all the water had been separated 5 which permits con/[humus oxypropyiation and owethYlaenough Xylene Was taken out to a the final Product tion. More specific reference will be made to treatment reflux for Several hours Somewhere In the {ange with glycide subseqeutnly in the text. The oxyethylation to 150 C., or thereabouts. Usually the mixture yielded step i of com-Se, h Same as the oxypmpylation Step a Clear Solutloll y the tlme thfi bulk of the Water, all insofar that two low boiling liquids are handled in each of the water, had been removed. 10 instance. What immediately follows refers to oxyethyla- Note that as pointed out previously, this procedure is tion and it is understood that oxypropylation can be hanillustrated by 24 examples in Table II. clled conveniently in exactly the same manner.

TABLE II 4 Strength of Reaction Max. Resin Amt. Solvent used and Reaction N A in (is damn nt iormaldeh de tune distill Ex 0 used m 9 use n u soln. and a int. am temp" O (hrs) temp.,0

2a 882 Ammo A, 176 g 30%, 200 g Xylene, 600 g 20-23 26 152 a 480 A Xylene, 450 g 2021 24 150 10a 633 -22 28 151 2a 441 20-28 36 144 5a 480 22-30 156 10a 1533 21-28 32 150 2a 882 21-23 145 5a 480 20-25 148 10a 633 20-27 35 143 13a 473 20-22 31 145 14a 511 21-26 24 140 1511 665 22-25 as 151 2a 441 25-33 32 150 6a 430 21-24 30 152 9a 595 21-26 27 145 2a 441 20-23 25 141 2a 480 22-27 20 143 1411 511 23-25 36 149 222 498 21-20 32 14a 2311 542 21-23 30 148 250 547 20-26 36 152 2a 441 21-24 32 i 150 2611 595 Amine H, 282 g 21-23 25 150 1a 391 Amine H, 141 g 30%, 50 g 21-22 28 151 As to the formulas of the above amines referred to as Amine A through Amine H, inclusive, see immediately below:

11 11 Amine Ncmnv o a o H:

Amine B No ,HN

can onr.

Amine 0- NOHN o H; o H:

NonsnNonim OH: H CH:

H H: Amine E- O NCzHrNC'zHs 11 0-0 Ha H:

n Amine r- 0111,, 0 ommuomomonm CH: CH! Amine G- NC2H4NC 3H|NC2H4N n H H H Amine H- CHr-CH: 0 H3011 onto-on HONH-O:H4NH--OH o-oom GH -O a GHr The oxyethylation procedure employed in the preparation of derivatives of the preceding .intermediates has been uniformly the same, particularly in light of the factthat a continuous operating procedure was employed. In this particular procedure the autoclave was a conventional jacketed autoclave, made of stainless steel and having a capacity of approximately 25 gallons, and a working pressure of 300 pounds gauge pressure. equipped With the conventional devices and openings, such as the variable speed stirrer operating at speeds from 50 R. P. M. to 500 R. P. M., therometer Well and thermocouple for recorder controller; emptying outlet, pressure gauge, manual and rupture disc vent lines; charge hole for initial reactants; at least one connection for conduct- .ing the incoming alkylene oxide, such as ethylene oxide, to the bottom of the autoclave; along with suitable devices for both cooling and heating the autoclave through the jacket. Also, I prefer coils in addition thereto, with the coils so arranged that they are suitable for heating with steam or cooling with Water, and the jacket further equipped with electrical heating devices, such as are employed for hot oil or Dowtherm systems. Dowtherm, more specifically Dowtherm A, is a colorless non-corrosive liquid consisting of an eutectic mixture of diphenyl and diphenyl oxide. Such autoclaves are, of course, in essence, small scale replicas of the usual conventional autoclave used in commercial oxyalkylating procedure.

Continuous operation, or substantially continuous operation, is achieved by the use of a separate container to hold the alkylene oxide being employed, particularly ethylene oxide. The container consists essentially of a laboratory bomb having a capacity of about 10 to 15 gallons or somewhat in excess thereof. This bomb was equipped, also, with an inlet for charging, and an outlet tube going to the bottom of the container so as to permit discharging of alkylene oxide in the liquid phase to the autoclave. Other conventional equipment consists, of course, of the rupture disc, pressure gauge, sight feed The autoclave was lowing:

21 connection for nitrogen for pres- The bomb was placed on a scale during use and the connections between the bomb and the autoclave were flexible Stainless hose or tubing so that continuous weighings could be made without breaking or making any connections. This also applied to the nitrogen line, which was used to pressure the bomb reservoir. To the extent that it was required, any other usual conventional procedure or addition which provided greater safety was used, of course, such as safety glass, protective screens, etc. i

With this particular arrangement practically all oxyethylations became uniform in that the reaction temperature could be held within a few degrees of any selected point in this particular range. In the early stages where the concentration of catalyst is high the temperature was generally set for around 130 C. or thereabouts. Subsequently the temperature may be somewhat higher for instance, 135 C. to 140 C. Under other conditions, definitely higher temperatures may be employed, for instance 170 C. to 175 C. It will be noted by examination of subsequent examples that this temperature range was satisfactory. in any case, where the reaction goes more slowly a higher temperature may be used, for instance, 140 C. to 145 (1., and if need be 150 C. to 160 C. incidentally, oxypropylation takes place more slowly than oxyethylation as a rule and for this reason we have used a temperature of approximately 130 C. to 140 C., as being particularly desirable for initial oxypropylation, and have stayed within the range of 130 C. to 135 C. almost invariably during oxypropylation. The lesser reactivity of propylene oxide compared with ethlene oxide can be offset by use of more catalyst, more vigorous agitation and perhaps a longer time period. The ethylene oxide was forced in by means of nitrogen pressure as rapidly as it was absorbed as indicated by the pressure gauge on the autoclave. in case the reaction slowed up the temperature was raised so as to speed up the reaction somewhat by use of extreme heat. It need be, cooling water was employed to control the temperature.

As previously pointed out in the case of oxypropylation as differentiated from oxyethylation, there was a tendency for the reaction to slow up as the temperature dropped much below the selected point of reaction, for instance, 135 C. In this instance, the technique employed was the same as before, that is, either cooling water was cut down or steam was employed, or the addition of propylene oxide speeded up, or electric heat used in addition to the steam in order that the reaction proceeded at, or near, the selected temperatures to be maintained.

inversely, if the reaction proceeded too fast regardless of the particular alkylene oxide, the amount of reactant being added, such as ethylene oxide, was cut down or electrical heat was cut oil, or steam was reduced, or if need be, cooling water was run through both the jacket and the cooling coil. All these operations, of course, are depending on the required number of conventional gauges, check valves, etc., and the entire equipment, as has been pointed out, is conventional and, as far as I am aware can be furnished by at least two firms who specialize in the manufacture of this kind of equipment.

Attention is directed to the fact that the useof glycide requires extreme caution. This is particularly true on any scale on or than small laboratory or semi-pilot plant operations. Purely from the standpoint of safety in the handling of glycide, attention is directed to the fol- {a} If prepared from glycerol monochlorohydrin, this product should be comparatively pure; (b) the glycide itself should be as pure as possible as the effect of impurities isdifficult to evaluate; (c) the glycide should be introduced carefully and precaution should be taken that it reacts as promptly as introduced, i. e.,

glass, thermometer, suring bomb, etc.

at racts that no excess of glycide is allowed to acumulate;" (d) all necessary precautions should be taken that glycide cannot polymerize per se; (e) due to the high boiling point of glycide one can readily employ a typical separatable glass resin pot as described in U. S. Patent No. 2,499,370,- dated March 7, 1950, and offered for sale by numerous laboratory supply houses. If such arrangement is used to prepare laboratory scale duplications, then care should be taken that the heating mantle can be removed rapidly so as to allow for cooling; or better still, through an added opening at the top, the glass resin pot or comparable vessel should be equipped with a stainless steel cooling coil so that the pot can be cooled more rapidly than mere removal of mantle. If a stainless steel coil is introduced it means that conventional stirrer of the paddle type is changed into the centrifugal type which causes the fluids or reactants to mix due to swirling action in the center of the pot. Still better, is the use of a laboratory autoclave of the kind previously described in this part of the text, but in any event, when the initial amount of glycide is added to a suitable reactant, such as the herein described amine-modified phenol-aldehyde resin, the speed of reaction should be controlled by the usual factors, such as (a) the addition of glycide; (b) theelimination of external heat, and (c) use of cooling coils so there is no undue rise in temperature. All the foregoing is merely conventional but is included due to the hazard in handling glycide.

Although ethylene oxide and propylene oxide may represent less of a hazard than glycide, yet these reactants should be handled with extreme care. One suitable procedure involves the use of propylene oxide or butylene oxide as a solvent as well as a reactant in the earlier stages along with ethylene oxide, for instance, by dissolving the appropriate resin condensate in propylene oxide even though oxyalkylation is taking place to a greater or lesser degree. After a solution has been obtained which represents the selected resin condensate dissolved in propylene oxide or butylene oxide, or a mixture which includes the oxyalkylated product, ethylene oxide is added to react with the liquid mass until hydrophile properties are obtained, if not previously present to the desired degree. Indeed hydrophile character can be reduced or balanced by use of some other oxide such as propylene oxide or butylene oxide. Since ethylene oxide is more reactive than propylene oxide or butylene oxide, the final product may contain some unreacted propylene oxide or butylene oxide which can be eliminated by volatilization or distillation in any suitable manner. See article entitled Ethylene oxide hazards and methods of handling, Industrial and Engineering Chemistry, volume 42, N0. 6, June 1950, pp. 1251-1258. Other procedures can be employed as, for example, that described in U. S. Patent 2,586,767, dated February 19, 1952, to Wilson.

Example In The oxyalkylation-susceptible compound employed is the one previously described and designated as Example 1b. Condensate lb was in turn obtained from symmetrical dimethylethylene diamine and the resin previously identified as Example 2a. Reference to Table I shows that this particular resin is obtained from paratertiarybutylphenol and formaldehyde. 10.82 pounds of this resin condensate were dissolved in 6 pounds of solvent (xylene) along with one pound of finely powdered caustic soda as a catalyst. Adjustment was made in the autoclave to operate at a temperature of approximately C. to C., and at a pressure of about 15 to 20 or 25 pounds, 25 pounds at the most. In some subsequent examples pressures. up to 35 pounds were employed. 4 p r I The time regulator was set so as to inject the ethylene oxide in approximately three-quarters of an hour and then continue stirring for '15 minutes or longer, a total time of one hour. The reaction went readily and, as a matter of fact, the oxide was taken up almost immediately. Indeed the reaction was complete in less than an hour. The speed of reaction, particularly at the low pressure, undoubtedly was due in a large measure to excellent agitation and also to the comparatively high concentration of catalyst. The amount of ethylene oxide introduced was equal in weight to the initial condensation product, to wit, 10.82 pounds. This represented a molal ratio of 24.6 moles of ethylene oxide per mole of condensate.

The theoretical molecular weight at the end of the reaction period was 2164. A comparatively small sample, less than 0 grams, was withdrawn merely for examination as far as solubility or emulsifying power was concerned and also for the purpose of making some tests on various oil field emulsions. The amount withdrawn was so small that no cognizance of this fact is included in the data, or subsequent data, or in the data presented in tabular form in subsequent Tables 3 and 4.

The size of the autoclave employed was 25 gallons. In innumerable comparable oxyalkylations I have with drawn a substantial portion at the end of each step and continued oxyalkylation on a partial residual sample. This was not the case in this particular series. Certain examples were duplicated as hereinafter noted and subjected to oxyalkylation with a different oxide.

Example 2c This example simply illustrates the further oxyalkylation of Example 10, preceding. As previously stated, the oxyalkylation-susceptible compound, to wit, Example l b, present at the beginning of the stage was obviously the same as at the end of the prior stage (Example 1c), to wit, 10.82 pounds. The amount of oxide present in the initial step was 10.82 pounds, the amount of catalyst remained the same, to wit, one pound, and the amount of solvent remained the same. The amount of oxide added was another 10.82 pounds, all addition of oxide in these various stages being based on the addition of this particular amount. Thus, at the end of the oxyethylation step the amount of oxide added was a total of 21.64 pounds and the molal ratio of ethylene oxide to resin condensate was 49.2 to 1. The theoretical. molecular weight was 3246.

The maximum temperature during the operation was 125 C. to 130 C. The maximum pressure was in the range of 15 to 25 pounds. The time period was one and three-quarter hours.

Example 3c Example 40 The oxyethylation was continued and the amount of oxide added again was 10.82 pounds. There was no added catalyst and no added solvent. The theoretical 'molecular weight at the end of the reaction period was 5410. The molal ratio 'of oxide to condensate was 98.4 to 1. Conditions as far as temperature and pressure were concerned were the same as in previous examples. The

time period was slightly longer, to wit, 2% hours. The reaction unquestionably began to slow up somewhat.

Example 5c The oxyethylation continued with the introduction of another 10.82 pounds of ethylene oxide. No more solvent was introduced but .3 pound caustic soda was added. The theoretical molecular weight at the end of the agitation period was 6492, and the molal ratio of oxide to resin condensate was 123 to 1. The time period, however, dropped to 2 hours. Operating temperature and pressure remained the same as in the previous example.

Example The same procedure was followed as in the previous examples. The amount of oxide added was another 10.82 pounds, bringing the total oxide introduced to 64.92 pounds. The temperature and pressure during this period were the same as before. There was no added solvent. The time period was 3 hours.

Example The same procedure was followed as in the previous six examples without the addition of more caustic or more solvent. The total amount of oxide introduced at the end of the period was 75.74 pounds. The theoretical molecular weight at the end of the oxyalkylation period was 8656. The time required for the oxyethylation was a bit longer than in the previous step, to wit, 4 hours.

Example 8c This was the final oxyethylation in this particular series. There was no added solvent and no added catalyst. The total amount of oxide added at the end of this step was 86.56 pounds. The theoretical molecular weight was 9738. The molal ratio of oxide to resin condensate was 196.8 to one. Conditions as far as temperature and pressure were concerned were the same as in the previous examples and the time required for oxyethylation was 5 hours.

The same procedure as described in the previous examples was employed in connection with a number of the other condensates described previously. All these data have been presented in tabular form in a series of four tables, Tables III and IV, V and VI.

In substantially every case a 25-gallon autoclave was employed, although in some instancesthe initial oxyethylation was started in a 15-gallon autoclave and then transferred to a 25-gallon autoclave. This is immaterial but happened to be a matter of convenience only. The solvent used in all cases was xylene. The catalyst used was finely powdered caustic soda.

Referring now to Tables Ill and IV, it will be noted that compounds 10 through 400 were obtained by the use of ethylene oxide, whereas 410 through 800 were obtained by the use of propylene oxide alone.

Thus, in reference to Table ill it is to be noted as follows.

The example number of each compound is indicated in the first column.

The identity of the oxyalkylation-susceptible compound, to Wit, the resin condensate, is indicated in the second column.

The amount of condensate is shown in the third column.

Assuming that ethylene oxide alone is employed, as happens to be the case in Examples 1e through 400, the amount of oxide present in the oxyalkylation derivative i'sshown in column 4, although in the initial step since no oxide is present there is a blank.

amass When ethylene oxide is used exclusively the th column is blank.

The 6th column shows the amount of powdered caustic soda used as a catalyst, and the 7th column shows the amount of solvent employed.

The 8th column can be ignored where a single oxide was employed.

The 9th column shows the theoretical molecular weight at the end of the oxyalkylation period.

The 10th column states the amount of condensate present in the reaction mass at the end of the period.

As pointed out previously, in this particular series the amount of reaction mass withdrawn for examination was so small that it was ignored and for this reason the resin condensate in column 10 coincides with the figure in column 3.

Column 11 shows the amount of ethylene oxide employed in the reaction mass at the end of the particular period.

Column 12 can be ignored insofar that no propylene oxide was employed.

Column 13 shows the catalyst at the end of the reaction period.

Column 14 shows the amount of solvent at the end of the reaction period.

Column 15 shows the molal ratio of ethylene oxide to condensate.

Column 16 can be ignored for the reason that no propylene oxide was employed.

Referring now to Table VI. It is to be noted that the first column refers to Examples 10, 20, 3c, etc.

The second column gives the maximum temperature employed during the oxyalkylation step and the third column gives the maximum pressure.

The fourth column gives the time period employed.

The last three columns show solubility tests by shaking a small amount of the compound, including the solvent present, with several volumes of water, xylene and kerosene. It sometimes happens that although xylene in comparatively small amounts will dissolve in the con centrated material, when the concentrated material in turn is diluted with xylene separation takes place.

Referring to Table IV, Examples 410 through 800 are the counterparts of Examples 1c through 400, except that the oxide employed is propylene oxide instead of ethylene oxide. Therefore, as explained previously, four columns are blank, to wit, columns 4, 8, 11 and 15.

Reference is now made to Table V. It is to be noted these compounds are designated by "(1" numbers, 1d, 2d, 3d, etc., through and including 32d. They are derived, in turn, from compounds in the 0 series, for example, 36c, 40c, 54c and 700. These compounds involve the use of both ethylene oxide and propylene oxide. Since compounds 10 through 400 were obtained by the use of ethylene oxide it is obvious that those obtained from 36c and 40c, involve the use of ethylene oxide first, and propylene oxide afterward. Inversely, those compounds obtained from 540 and 700 obviously come from a prior series in which propylene oxide was used first.

In the preparation of this series indicated by the small letter d, as 1d, 2d, 3d, etc., the initial 0 series such 36c, 40c, 54c, and 700, were duplicated and the oxyalkylation stopped at the point designated instead of being carried further as may have been the case in the original oxyalkylation step. Then oxyalkylation proceeded by using the second oxide as indicated by the previous ex planation, to wit, propylene oxide in 1d through 16d, and,

ethylene oxide in 17d through 32d, inclusive.

In examining the table beginning with 1d, it will be noted that the initial product, i. e., 360, consisted of the reaction product involving 10.82 pounds of the resin condensate, 16.23 pounds of ethylene oxide, 1.0 pound of caustic soda, and 6.0 pounds of the solvent.

It is to be noted that reference to the catalyst in Table 26 V refers to the total amount of catalyst, i. e., the catalyst present from the first oxyalkylation step plus added catalyst, if any. The same is true in regard to the solvent. Reference to the solvent refers to the total solvent present, i. e., that from the first oxyalkylation step plus added solvent, if any.

In this series, it will be noted that the theoretical molecular weights are given prior to the oxyalkyation step and after the oxyalkylation step, although the value at the end of one step is the value at the beginning of the next step, except obviously at the very start the value depends on the theoretical molecular weight at the end of the initial oxyalkylation step; i. e., oxyethylation for 1d through 16d, and oxypropylation for 17d through 382d.

It will be noted also that under the molal ratio the values of both oxides to the resin condensate are included.

The data given in regard to the operating conditions is substantially the same as before and appears in Table VI.

The products resulting from these procedures may contain modest amounts, or have small amounts, of the solvents as indicated by the figures in the tables. If desired the solvent may be removed by distillation, and particularly vacuum distillation. Such distillation also may remove traces or small amounts of uncombined oxide, if present and volatile under the conditions employed.

Obviously, in the use of ethylene oxide and propylene oxide in combination one need not first use one oxide and then the other, but one can mix the two oxides and thus obtain what may be termed an indifferent oxyalkylation, i. e., no attempt to selectively add one and then the other, or any other variant.

Needless to say, one could start with ethylene oxide and then use propylene oxide, and then go back to ethylene oxide; or, inversely, start with propylene oxide, then use ethylene oxide, and then go back to propylene oxide; or, one could use a combination in which butylene oxide is used along with either one of the two oxides just mentioned, or a combination of both of them.

The colors of the products usually vary from a reddish amber tint to a definitely red, and amber. The reason is primarily that no effort is made to obtain colorless resins initially and the resins themselves may be yellow, amber, or even dark amber. Condensation of a nitrogenous product invariably yields a darker product than the original resin and usually has a reddish color. The solvent employed, if xylene, adds nothing to the color but one may use a darker colored aromatic petroleum solvent. Oxyalkylation generally tends to yield lighter colored products and the more oxide employed the lighter the color of the product. Products can be prepared in which the final color is a lighter amber with a reddish tint. Such products can be decolorized by the use of clays, bleaching chars, etc. As far as use in demulsification is concerned, or some other industrial uses, there is no justification for the cost of bleaching the product.

Generally speaking, the amount of alkaline catalyst present is comparatively small and it need not be removed. Since the products per se are alkaline due to the presence of a basic nitrogen, the removal of the alkaline catalyst is somewhat more difficult than ordinarily is the case for the reason that if one adds hydrochloric acid, for example, to neutralize the alkalinity one may partially neutralize the basic nitrogen radical also. The preferred procedure is to ignore the presence of the alkali unless it is objectionable or else add a' stoichiometric amount of concentrated hydrochloric acid equal to the caustic soda present.

TABLE V Composition before 1 Composition at end Molal ratio 3 ,3 o-s' Ethyl. Propl. Gate.- So1- Theo. Theo. o-s* Ethyl. Prppl. (Jata- Sol- Em Pm 1 ex. cmpd., oxide, oxide, lyst, vent, mol. mol. cmpd., oxide, oxlde, lyst, vent, g No lbs. lbs. lbs. lbs. lbs. wt. wt. lbs. lbs. lbs. lbs. lbs. to resin to resin condencondensate sate 36c 10. 82 21. 64 1. 0 6. 0 3, 246 3, 787 10. 82 21. 64 5. 41 1. 0 6. 0 49. 2 9. 33 36c 10. 82 21.64 5.41 1.0 6.0 3, 787 4,328 10. 82 21.64 10. 82 1.0 6.0 49.2 18.66 360 10. 82 21.64 10. 82 1.0 6.0 4, 328 4,869 10. 82 21.64 16. 23 1.0 6.0 49.2 27.90 360 10. 82 21. 64 16.23 1. 0 6. 0 4, 869 5, 410 10. 82 21. 64 21.64 1. 0 6. 0 49. 2 37. 35 36c 10. 82 21.64 21. 64 1. 0 6. 0 5, 410 6, 933 10. 82 21.64 37. 87 1. 0 6. 0 49. 2 65. 30 36c 10. 82 21.64 37.87 1.5 6.0 6, 933 8,015 10.82 21.64 48.69 1. 6.0 49. 2 83.9 36c 10. 82 21.64 48.69 1.5 6.0 8,015 8, 556 10. 82 21.64 54.10 1.5 6.0 49.2 93.3 360 10. 82 21.64 54. 1. 5 6. 0 8, 556 9,097 10. 82 21.64 59. 51 1. 5 6. 0 49. 2 102. 5 400 10. 82 43. 28 1. 3 6. 0 5, 410 5, 951 10. 82 43. 28 5. 41 1. 3 6. 0 98. 4 9.33 400 10. 82 43. 28 5. 41 1. 3 6. 0 5, 951 6, 492 10. 82 43. 28 10. 82 1. 3 6. 0 98. 4 18. 66 40c 10. 82 43.28 10. 82 1.3 6.0 6,492 7,033 10.82 43.28 16.23 1.3 6.0 98.4 28.00 40c 10.82 43.28 16.23 1.3 6.0 7,033 8,115 10.82 43.28 27. 05 1.3 6.0 98. 4 46. 60 406 10.82 43.28 27.05 1.3 6.0 8,115 10,279 10. 82 43. 28 48.69 1.8 6.0 98.4 83.90 400 10. 82 43. 28 48. 69 1. 8 6. 0 10, 279 10, 820 10. 82 43. 28 54. 10 1. 8 6. 0 98. 4 93. 3 400 10. 82 43. 28 54. 10 1. 8 6. 0 10. 820 11,361 10. 82 43. 28 59. 51 1. 8 6. 0 98. 4 102. 5 400 10. 82 43. 28 59. 51 1. 8 6. 0 11,361 11, 902 10. 82 43. 28 64. 92 1. 8 6. 0 98. 4 111. 8 540 11.88 83.16 1.4 4. 5 10,692 11,286 11.88 5.94 83.16 1.4 4.5 13. 5 143. 5 54c 11.88 83.16 1. 4 4.5 11,286 11. 880 11.88 11.88 83.16 1.4 4.5 26.9 143. 5 546 11. 88 83.16 1. 4 4. 5 11, 880 12, 474 11. 88 17.82 83. 16 1. 4 4. 5 40. 5 143. 5 546 11.88 83.16 1.4 4.5 12,474 13,068 11.88 23. 76 83.16 1.4 4. 5 54.0 143.5 546 11.88 83.16 1.4 4.5 13,068 13,662 11.88 29.70 83.16 1.4 4. 5 67. 5 143.5 546 11.88 83.16 1.4 4. 5 13,662 14, 256 11. 88 35.66 83.16 1. 4 4. 5 81.0 143. 5 540 11. 88 83.16 1. 4 4. 5 14, 256 14,850 11. 88 41. 58 83.16 1. 4 4. 5 94. 5 143. 5 540 11. 88 83.16 1.4 4. 5 14,850 15, 444 11.88 47. 52 83.16 1. 4 4. 5 108.0 143. 5 70c 14.56 101.92 1. 5 5.0 13,104 13 468 14, 56 3.64 101. 92 1. 5 5.0 8. 28 175.7 700 14.56 101.92 1.5 5.0 13,468 13,832 14.56 7.28 101.92 1.5 5.0 16. 56 175.7 700 14. 56 101.92 1. 5 5.0 13,832 14, 560 14.56 14.56 101.92 1. 5 5.0 10 175. 7 706 14.56 101. 92 1. 5 5. 0 560 14,924 14, 56 18. 101. 92 1. 5 5. 0 41. 175. 7 700 14.56 101.92 1. 5 5. 0 14, 924 15,288 14.56 21.84 101. 1. 5 5.0 49.60 175.7 700 14. 56 101. 92 1. 5 5. 0 15, 288 16, 016 14. 56 29. 12 101. 92 1. 5 5. 0 66. 20 175. 7 700 14.56 101.92 1. 5 5.0 16,016 16,744 14.56 36.40 101.92 1. 5 5.0 82.80 175.7 700 14.56 36. 101. 92 1. 5 5. 0 16, 744 18,000 14.56 50. 96 101.92 1. 5 5. 0 115. 8 175.7 Oxyalkylation-suseeptible.

TABLE VI TABLE VI-Contlnued Solubility Max Max Solubility Ex Max. Max. Time Time, temp., pres., N temp, p1es., h NO. 0 O s 1 hrs. o C p s 1 Water Xylene Kerosene Kerosene TC 125-130 15-25 1 Insoluble -1 5-18 1 0 2 Insoluble. 26 125-130 15-25 1% Emulsl'fiable. 8 -1 3 15-20 Do. 3 125-130 15-25 2 Soluble 59C.- 125-135 15-20 3 D0. 4 125-130 1545 2 d 600.. 125-135 15-20 4 D 5 125-130 16-25 2 do 610.. 125-135 15-20 4 Do. 125-130 15-25 3 d0 6 1 5-18 15 0 3% Soluble. 711., 125-130 15-25 4 d0 630.. 125-135 15-20 4 0' 125-130 15-25 5 ov 646.. 125-135 15-20 5 125-135 20-25 1 Insoluble. 30- 0 5-10 /5 Insoluble 125-135 20-25 660.. 130-140 5-10 2% 110 125-135 20-25 670.. 130-140 5-10 3 Do. 125 125-135 20-25 680.. 130-140 5-10 4 Soluble. 13 125-135 20-25 690.. 130-140 5-10 5 14 125-135 20-25 700.. 130-140 5-10 4 13,, 15:: 125-135 20-25 710.. 130-140 5-10 5 D0. 16 125-135 20-25 726.. 130-140 5-10 6 D 17c 125-135 15-25 73c.. 125-130 15-20 1 Insoluble 180. 125-135 15-25 740.. 125-130 15-20 2 196 125-135 15-25 c..125-130 15-20 2 20 -135 15-25 760.. 125-130 15-20 D 210 125-135 15-25 77c.. 125-130 15-20 DO. 220 125-135 15-25 780.. 125-130 15-20 Soluble. 23c 125-135 15-25 790.. 125-130 15-20 24 125-135 15-25 800.. 125-130 15-20 D 250 -135 15-20 55 1d-- 130-135 20-30 Insoluble 260 130-135 15-20 211-- 130-135 20-30 D0. 27 130-135 15-20 31L- 130-135 20-30 D 280 1311- 15-20 411.. 130-135 20-30 29 130-135 15-20 5d. 130-135 20-30 D 300 130-135 15-20 611-- 130-135 20-30 31 130-135 15-20 711.. 130-135 20-30 D 32c 130-135 15-20 811-. 130-135 20-30 g 33c 130-135 20-30 10 911.- 130-135 20-30 Insoluble 34 130-135 20-30 10d 130-135 20-30 1) 35 1110-135 20-30 1111 130-135 20-30 360 1130-135 -30 12d 130-135 20-30 D 37 130-135 20-30 1311. 130-135 20-30 1), 33 130-135 20-30 1471 130-135 20-30 D 395 130-135 20-30 15d. 130-135 20-30 D 40 130-135 20-30 6 16d. 130-135 20-30 D 41; 125-135 20-25 1 Insoluble. 5 17d. 130-135 30-35 s l 42 125-135 20-25 1 D0. 1811 130-135 30-35 D 43 125-135 20-25 1% 0 19d 130-135 30-35 D 44 125-135 20-25 2 Soluble 2011. 1311-135 30-35 1) 45a 125-135 20-25 3 0 21d 130-135 30-35 Di b1 460 125-135 20-25 3 D0 22d. 130-135 30-35 Insoluble. 470 125-135 20-25 3 Do 23d- 130-135 30-35 48., 125-135 20-25 3 o 70 24d- 130-135 30-35 49 130-135 30-35 2 Insoluble 25d. 130-140 5-10 s l bl 50 130-135 30-35 2% 0 2611 130-140 5-10 D 510 130-135 30-35 3 0 27d- 130-140 5-10 1), 52 130-135 30-35 4 Soluble 28d 130-140 5-10 D 53 130-135 30-35 4% 0 29d 130-140 5-10 D 54c 130-135 30-35 3 D0 3011 130-140 5-10 Dj ib1 556 130-135 30-35 4 D0. 31d. 130-140 5-10 Insoluble. 56c 130-135 30-35 5 D0. 7 32d- 130-140 5-10 D 31 PART The products described in Part 4 have utility in at least two distinct ways-the products as such or in the form of some simple derivative, such as the salt, which can be used in numerous arts subsequently described. Also, the products can serve as initial materials for more complicated reactions of the kind ordinarily involving a hydroxyl radical. This includes esterification, etherization, etc. Likewise, the group including the nitrogen atom can be reacted with suitable reactants such as chloroacetic acid esters, benzyl chloride, alkyl halides, esters of sulfonic acids, methyl sulfate, or the like, so as to give new ammonium compounds which may be used, not only for the purpose herein described, but also for various other uses.

The products herein described as such and prepared in accordance with this invention can be used as emulsi- 'fying agents, for oils, fats, and waxes, as ingredients in insecticide compositions, or as detergents and wetting agents in the laundering, scouring, dyeing, tanning and mordanting industries. They may also be used for preparing boring or metal-cutting oils and cattle dips, as metal pickling inhibitors, and for pharmaceutical purposes.

Other uses include the preparation or resolution of petroleum emulsions, whether of the water-in-oil type or oil-in-water type. They may be used as additives in connection with other emulsifying agents; they may be employed to contribute hydrotropic effects; they may be used as anti-strippers in connection with asphalts; they may be used to prevent corrosion, particularly the corrosion of ferrous metals for various purposes and particularly in connection with the production of oil and gas, and also in refineries where crude oil is converted into various commercial products. The products may be used industrially to inhibit or stop micro-organic growth or other objectionable lower forms of life, such as the growth of algae, or the like; they may be used to inhibit the growth of bacteria, molds, etc.; additives to lubricating oils, both those derived from petroleum and synthetic lubricating oils, and also to bydraulic brake fluids of the aqueous or nonaqueous type, some have definite anti-corrosive action, they may be used in connection with other processes where they are injected into an oil or gas well for purpose of removing a mud sheath, increasing the ultimate flow of fluid from the surrounding strata, and particularly in secondary recovery operations using aqueous flood waters, and for use in dry cleaners soaps.

With regard to the above statements, reference is made particularly to the use of the materials as such, or in the form of a salt; the salt form refers to a salt involving either one, two or more of the basic nitrogen atoms. Obviously, the salt form involves a modification in which the hydrophile character can either be increased or decreased and, inversely, the hydrophobe character can be decreased or increased. For example, neutralizing the prodnet with practically any low molal acid, such as acetic acid, hydroxy acetic acid, lactic acid, or nitric acid, is apt to markedly increase the hydrophile efi'ect. One may also use acids of the type in which R is a comparatively small alkyl radical, such as methyl, ethyl or propyl. The hydrophile effect may be decreased and the hydrophobe effect increased by neutralization with a monocarboxy detergent-forming acid. These are acids which have at least 8 and not more than 32 carbon atoms. They are obtained from higher fatty acids and include also resin acids such as abietic acid, and petroleum acids such as naphthenic acids and acids obtained by the oxidation of wax. 'One can also obtain new products having unique properties by combination with polybasic acids, such as diglycolic acid, oxalic acid, dimerized acids from linseed oil, etc. The most common they are valuable examples, of course, are the higher fatty acids having generally 10 to 18 carbon atoms. I have found that a particularly valuable anti-corrosive agent can be obtained from any suitableresin and formaldehyde provided the polyamine includes one or more cyclohexyl radicals. The corrosiondnhibiting properties of such compound can be increased by neutralization with either one or two moles of an oil-soluble sulfonic acid, particularly a sulfonic acid of the type known as mahogany sulfonic acid.

The oil-soluble sulfonic acids previously referred to may be synthetically derived by sulfonating olefine, aliphatic fatty acids, or their esters, alkylated aromatics or their hydroxyl derivatives, partially hydrogenated aromatics, etc., with sulfuric acid or other sulfonating agents. However, the soaps of so-called mahogany acids which are usually produced during treatment of lubricating oil distillates with concentrated sulfuric acid or higher concentration) remain in the oil after settling out sludge. These sulfonic acids may be represented as where (R) is one or more alkyl, alkaryl or aralkyl groups and the aromatic nucleus may be a single or condensed ring or a partially hydrogenated ring. The lower molecular weight acids can be extracted from the acid-treated oil by adding a small amount of water, preferably after dilution of the oil with kerosene. However, the more desirable high molecular weight (350-500) acids, particularly those produced when treating petroleum distillates with fuming acid to produce white oil, are normally recovered as sodium soaps by neutralizing the acid oil with sodium hydroxide or carbonate and extracting with aqueous alcohol. The crude soap extract is first recovered as a water curd after removal of alcohol by distillation and a gravity separation of some of the contaminating salts (sodium carbonate, sulfates and sulfites). These materials still contain considerable quantities of salts and consequently are normally purified by addition of a more concentrated alcohol followed by storage to permit settling of salt brine. The alcohol and Water are then stripped out and the sodium salts so obtained converted into free acids.

Not only can one obtain by-product sulfonic acids of the mahogany type which are perfectly satisfactory and within the molecular range of 300 to 600 but also one can obtain somewhat similar materials which are obtained as the principal product of reaction and have all the usual characteristics of normal by-product sulfonic acids but in some instances contain two sulfonic groups, i. e., are disulfonic acids. This type of mahogany acid or, better still, oil-soluble sulfonic acid, is perfectly satisfactory for the above described purpose.

Much of what has been said previously is concerned with derivatives in which the hydrophile properties are enhanced in comparison with the resin as such. A procedure designed primarily to enhance the hydrophobe properties of the resin involves derivatives obtained by a phenyl or substituted phenyl glycidyl etherof the structure in which R represents a hydrocarbon substituent such as an alkyl radical having 1 to 24 carbon atoms, or a cyclic group, such as a cyclohexyl group, a phenyl group, or a benzyl group, and n represents 0, 1, 2 or 3. n is zero in the instance of the unsubstituted phenyl radical. Such compounds are in essence oxyalkylating agents and reaction involves the introduction of a hydrophobe group and the formation of an alkanol hydroxyl radical.

The compounds herein described and particularly those adapted for breaking petroleum emulsions, although having other uses as herein noted, are derived from resins in which the bridge between phenolic nuclei is a methylene group or a substituted methylene group.

Comparable amine-modified compounds serving all these various purposes are obtainable from another class of resins, i. e., those in which the phenolic nuclei are separated by a radical having at least a 3-carbon atom chain and are obtained, not by the use of a single aldehyde but by the use of formaldehyde, in combination with a carbonyl compound selected from the class of aldehydesand ketones in which there is an alpha hydrogen atom available as in the case of acetaldehyde or acetone. Such resins almost invariably involve the use of a basic catalyst. Such bridge radicals between phenolic nuclei have either hydroxyl radicals or carbonyl radicals, or both, and are invariably oxyalkylation-susceptible and may also enter into more complicated reactants with basic secondary amines. The bridge radical in the initial resin has distinct hydrophile character. Such resins or compounds which can be converted readily into such resins are described in the following patents. Such analogous compounds are not included as part of the instant invention.

U. S. Patent Nos. 2,191,802, dated February 27, 1940, to Novotny et al.; 2,448,664, dated September 27, 1948, to Fife et al.; 2,538,883, dated January 23, 1951, to Schrimpe; 2,538,884, dated January 23, 1951, to Schrimpe; 2,545,559, dated March 20, 1951, to Schrimpe; 2,570,389, dated October 9, 1951, to Schrimpe.

See my co-pending applications, Serial Nos. 301,803, 301,804, 301,806, and 301,807, all filed July 30, 1952.

Having thus described my invention what I claim as new and desire to secure by Letters Patent, is

1. The process of first condensing (a) an oxyalkylationsusceptible, fusible, nonoxygenated organic solvent-soluble, water-insoluble, low-stage phenolaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atomsand reactive toward said phenol; said resin being formed in the substantial absence of phenols of functionality greater than 2; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms which is substituted in one of the 2, 4, and 6-positions of the phenolic nucleus; (b) a basic nonhydroxylated polyamine having at least one secondary amino group andhaving not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the poly amine be free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical; and formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; the molar ratio of the reactants a, b and 0 being approximately 122:2, respectively and with the proviso that the resinous condensation product resulting from the process be heatstable and oxyalkylation-susceptible; thereafter oxyalkylating the resulting condensation product by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

2. The process of first condensing (a) an oxyethylationsusceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to m'ethylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of phenols of functionality greater than 2; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms which is substituted in one of the 2, 4, and 6-positions of the phenolic nucleus; (b) a basic nonhydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the added proviso that the ratio of reactants be'approxirnately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; thereafter oxyalkylating said condensation product by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

3. The process of claim 1 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination.

4. The process of claim 2 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination.

5. The product resulting from the process defined in claim 1.

6. The product resulting from the process defined in claim 2.

7. The product resulting from the process defined in claim 3.

8. The product resulting from the process defined in claim 4.

References Cited in the file of this patent UNITED STATES PATENTS 

1. THE PROCESS OF FIRST CONDESNING (A) AN OXYALKYLATIONSUSCEPTIBLE, FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOLALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOLFORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF PHENOLS OF FUNCTIONALITY GREATER THAN 2; SAID PHENOL BEING OF THE FORMULA 